Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)
Abstract
Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF3) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−Rf bond formations (Rf = F, CF3) are commonly hampered by multiple factors (low nucleophilicity of the F− anion, strong M−CF3 bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−Rf bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF3 couplings taking place from structurally characterized MIVRf species (M = Ni, Pd, Pt; Rf = F, CF3). The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ MIVRf species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.
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BibTeX
@article{demonti2026arene,
title = {{Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)}},
author = {Luca Demonti and Hana Tabikh and Noel Nebra},
journal = {Coordination Chemistry Reviews},
year = {2026},
month = jul,
doi = {10.1016/j.ccr.2026.217739},
url = {https://hal.science/hal-05722045v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)
AU - Luca Demonti
AU - Hana Tabikh
AU - Noel Nebra
PY - 2026
DA - 2026/07/15
JO - Coordination Chemistry Reviews
DO - 10.1016/j.ccr.2026.217739
UR - https://hal.science/hal-05722045v1
AB - Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF3) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−Rf bond formations (Rf = F, CF3) are commonly hampered by multiple factors (low nucleophilicity of the F− anion, strong M−CF3 bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−Rf bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF3 couplings taking place from structurally characterized MIVRf species (M = Ni, Pd, Pt; Rf = F, CF3). The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ MIVRf species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.
SN - 0010-8545
SN - 0010-8545
ER -